Unique Multi-Hetero-Interface Engineering of Fe-Doped Co-LDH@MoS2-Ni3S2 Nanoflower-Based Electrocatalyst for Overall Water-Splitting: An Experimental and Theoretical Investigation.

Herein, a self-supported, robust, and noble-metal-free 3D hierarchical interface-rich Fe-doped Co-LDH@MoS2-Ni3S2/NF heterostructure electrocatalyst has been prepared through a controllable two-step hydrothermal process. The resultant electrode shows low overpotential of ~95 mV for hydrogen evolution reaction (HER), ~220 mV for the oxygen evolution reaction (OER), and the two-electrode system requires only a cell voltage of ~1.54 V at 10 mA cm-2 current density, respectively. Extensive ab initio calculations were carried out to find out the overpotential for HER, orbital interaction through the determination of electron density of states and quantification of charge transfer by Bader charge analysis. The computed overpotential matched closely with the experimental data. The superior HER performance of the tri-layer is enhanced due to the charge transfer (1.7444 e) to Fe-doped Co-LDH from Ni3S2-MoS2 hybrid. This research strategy paves an effective pathway for affordable green H2 production and future efficient non-precious bifunctional electrocatalyst design for overall water electrolysis.

Metal-organic framework-derived advanced oxygen electrocatalysts as air-cathodes for Zn-air batteries: recent trends and future perspectives.

Electrochemical energy storage devices with stable performance, high power output, and energy density are urgently needed to meet the global energy demand. Among the different electrochemical energy storage devices, batteries have become the most promising energy technologies and ranked as a highly investigated research subject. Recently, metal-air batteries especially Zn-air batteries (ZABs) have attracted enormous scientific interest in the electrochemical community due to their ease of operation, sustainability, environmental friendliness, and high efficiency. The oxygen electrocatalytic reactions [oxygen reduction reaction (ORR) and oxygen evolution reaction (OER)] are the two fundamental reactions for the development of ZABs. Noble metal-based electrocatalysts are widely considered as the benchmark for oxygen electrocatalysis, but their practical application in rechargeable ZAB is hindered due to several shortcomings. Thus, to replace noble metal-based catalysts, a wide range of transition-metal-based materials and heteroatom-doped metal-free carbon materials has been extensively investigated as oxygen electrocatalysts for ZABs. Recently, metal-organic frameworks (MOFs) with unique structural flexibility and uniformly dispersed active sites have become attractive precursors for the synthesis of a large variety of advanced functional materials. Herein, we summarize the recent progress of MOF-derived oxygen electrocatalysts (MOF-derived carbon nanomaterials, MOF-derived alloys/nanoparticles, and MOF-derived single-atom electrocatalysts) for ZABs. Specifically, we highlight MOF-derived single-atom electrocatalysts owing to the wide exploration of these emerging materials in electrocatalysis. The influence of the active sites, structural/compositional design, and porosity of MOF-derived advanced materials on the oxygen electrocatalytic performances is also discussed. Finally, the existing challenges and prospects of MOF-derived electrocatalysts in ZABs are briefly highlighted.